Sulfonediimine compounds



United States Patent US. Cl. 260-551 5 Claims This invention relates tonovel sulfonediimine detergents and to detergent compositions containingthese compounds.

There are several properties that are regarded as being essential for acompound to be suitable for use as a detergent. Foremost, is thecleaning ability of the compound, i.e., its ability to remove soil,e.g., from soiled clothes. In addition, the detergent should remain inactive form under conditions of usage, for example, at high temperaturessuch as 140 F. and in aqueous solutions. Although there are a number oforganic detergents which have these properties, detergent compounds suchas those of the present invention which have additional desirableproperties find wider scope of application.

The novel sulfonediimine compounds of this invention clean as well astetrapropylene benzene sulfonate. They are thermally stable andresistant to hydrolysis under conditions ordinarily encountered duringwashing. In addition, they are compatible with anionic, nonionic,zwitterionic, ampholytic, and cationic detergents; and in combinationwith anionic detergents such as dodecyl benzene sulfonate havesynergistic mildness properties.

The sulfonediimine compounds of this invention have the followingstructural formula:

wherein R is an aliphatic radical containing from about to about 18carbon atoms and R is a methyl or ethyl radical. The aliphatic radical Rcan be saturated or unsaturated and branched or straight chain.Preferably, -R is saturated and straight chain.

Examples of the compounds of this invention are:

methyl decyl sulfonediimine; ethyl decyl sulfonediimine; methyl dodecylsulfonediimine; methyl tetrapropylene sulfonediimine; methyl dodecenylsulfonediimine; ethyl dodecyl sulfonediimine; methyl tridecylsulfonediimine; methyl tetradecyl sulfonediimine; ethyl tetradecylsulfonediimine; ethyl pentadecyl sulfonediimine; methyl hexadecylsulfonediirnine; ethyl hexadecyl sulfonediimine; methyl octadecylsulfonediimine; methyl oleyl sulfonediimine; ethyl octadecylsulfonediimine.

It is believed that symmetrical short chain sulfonediimines have beenprepared in the prior art. It is surprising to find, however, that theparticular unsymmetrical sulfonediimines described above have highlydesirable properties for use as organic detergents.

It appears that only certain sulfonediimines have the aforementioneddesired properties; in these certain sulfonediimines, R and R must be asdescribed above. If R is longer in chain length than 18 carbon atoms orshorter in chain length than 10 carbon atoms, desired detergencycharacteristics are not obtained. Likewise, if R contains 3,445,515Patented May 20, 1969 "ice more than two carbon atoms, desireddetergency characteristics are not obtained.

The most preferred sulfonediimines are the C C methyl sulfonediimines.Particularly desirable is dodecyl methyl sulfonediimine since itexhibits a high degree of water solubility.

sulfonediimines of this invention can be prepared by reacting achloramine-ammonia mixture with dialkyl sulfides in an inert polarsolvent at a temperature ranging from about -20 C. to about 40 C. Ingeneral, reaction times ranging from about 5 hours to about 30 hours areemployed. Preferably, a reaction temperature ranging from about 5 C. toabout +5 C. and reaction times ranging from about 15 hours to about 20hours are employed. Preferably the molar ratio of chloramine to dialkylsulfide ranges from about 3:1 to about 5:1 and is most preferably about4:1. If molar ratios of chloramine to dialkyl sulfide of less than about3 :1 are employed herein the yield of product is too low for a practicalprocess; molar ratios in excess of about 5:1 produce only slightlyhigher yields than those obtained by employing the above specified molarratio range.

The molar ratio of ammonia to chloramine in the above chloramine-ammoniamixture can range from about 1:1 to about 20:1 or even higher. Thischloramine-ammonia mixture is conveniently prepared by the Sislertechnique described in Sisler, Neth and Hurley, The Journal of theAmerican Chemical Society, 76, 3906 (1954).

The dialkyl sulfides for use herein have the formula RRS wherein R and Rare defined as previously. These dialkyl sulfides are not readilyavailable commercially. They can be conveniently prepared by reactingalkyl mercaptans such as methyl mercaptan with alpha-olefins, such asfor example, l-dodecene in the presence of a free radical initiationcatalyst, such as azobisisobutyronitrile, benzoyl peroxide,tertiary-butyl perbenzoate, di-tertiarybutyl peroxide, or ultravioletlight.

The solvent for use herein must be very polar. It must dissolve thesulfide, be substantially unreactive, and promote displacementreactions. Examples of such solvents are acetonitrile, propionitrile,chloroform, methylene chloride, and lower C -C alcohols, such as forexample isopropanol.

The following equation represents a typical example of the reaction ofthis process:

acetonitrlle Compounds of this invention are useful per se as detergentand surface active agents. Desirably they are used withother materialsto form detergent compositions, as for example, liquid, bar, tablet,granular or other compositions. Such detergent compositions can containthe sulfonediimines of this invention, and water-soluble inorganicalkaline builder salts, water-soluble organic alkaline sequestrantbuilder salts or mixtures thereof in a ratio of sulfonediimine tobuilder salt of about 4:1 to about 1:20. Such detergent compositionsordinarily contain from 5% to 50% of detergent active and from 5% to ofbuilder salt.

Granular detergent compositions preferably contain about 5% to about 50%of the sulfonediimines of this invention and liquid formulationspreferably contain from about 2% to about 30% of such sulfonediimines.Granular detergents preferably contain at least an equal amount of analkaline builder salt. Liquid formulations preferably contain from about5% to about 40% of a water-soluble alkaline builder salt, the balance ofthe composition being a solvent such as water, and/ or other liquidvehicles. Liquid formulations can also contain a hydrotropingelectrolyte, e.g., sodium toluene sulfonate. All percentages and partsherein are by weight unless specified otherwise.

Water-soluble inorganic alkaline builder salts which can be used in thisinvention alone or in admixture are alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates and silicates. Ammonium orsubstituted ammonium, e.g., triethanol ammonium, salts of thesematerials can also be used. Specific examples of suitable salts aresodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodiumand potassium pyrophosphate, sodium and ammonium bicarbonate, potassiumtripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodiumorthophosphate and potassium bicarbonate. The preferred inorganicalkaline builders according to this invention are alkali metaltripolyphosphates for built granular and tablet compositions and alkalimetal pyrophosphates for built liquid compositions. Potassium is thepreferred alkali metal used in liquid compositions and sodium finds bestapplication for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used inthis invention alone or in admixture are alkali metal, ammonium orsubstituted ammonium, aminocarboxylates, e.g., sodium and potassiumethylenediaminetetraacetate, sodium and potassiumN-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassiumnitrilotriacetates and sodium, potassium and triethanolammoniumN-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of thesepolycarboxylates are also suitable. The alkali metal salts of phyticacid, e.g., sodium phytate are also suitable as organic alkalinesequestrant builder salts (see US. Patent 2,739,942). Also suitable asorganic alkaline sequestrant builder salts are the water-soluble saltsof polycarboxylate polymers and copolymers as described in the copendingapplication of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1963(e.g., polymers of itaconic acid, aconitic acid, maleic acid, mesaconicacid, fumaric acid, methylene malonic acid, and citronic acid andcopolymers with themselves and other compatible monomers such asethylene).

Polyphosphonates are also valuable builders in terms of the presentinvention, including specifically sodium and potassium salts ofethane-l-hydroxy-1,1-diphosphonate, sodium and potassium salts ofmethylene diphosphonate, sodium and potassium salts of ethylenediphosphonate, and sodium and potassium salts ofethane-1,1,2-triphosphonate. Other examples include the alkali metalsalts of ethane-2-carboxy-l,l-diphosphonic acid,hydroxymethanediphosphonic acid, carbonyldiphosphonic acid,ethanel-hydroxy- 1 1,2-triphosphonic acid, ethane-2-hydroxy-1, 1 2triphosphonic acid, propane l,1,3,3 tetraphosphonic acid,propane-1,1,2,3-tetraphosphonic acid and propane 1,2,2,3-tetraphosphonicacid.

Besides the builders being used together with sulfodiimines, it is alsopossible according to the present invention to use the sulfonediiminecompounds of this invention in combination with other cleaning agentssuch as anionic, ampholytic, Zwitterionic, and other nonionic organicdetergent surfactant compounds. When it is desired to use suchsulfonediimine compounds in combination with other detergent compounds,they are preferably utilized with anionic detergents because of thesudsing characteristics of the latter. The ratio of the sulfonediimineto such other detergent compound is from about 10:1 to 1:5. If it isdesired to use such a sulfonediimine in admixture with another detergentcompound as the active portion of a cleaning composition, the ratio ofsuch a mixture to the builder salt should be within the previouslyprescribed range of 4:1 to 1:20. A composition prepared along theselines can contain from 5% to 50% of such a mixture and 5% to 85% of abuilder salt selected from watersoluble inorganic alkaline buildersalts, water-soluble organic sequestrant builder salts, and mixturesthereof, within the prescribed ratio range.

Examples of anionic soap detergents which can be used taurides,alkylbenzenesulfonates wherein the alkyl substituent is straight chainor branched chain, sulfonated alphaolefins; alkylphenol polyethenoxysulfonates. In these compounds the alkyl and acyl groups, respectively,contain 10 to 20 carbon atoms. They are used in the form of watersolublesalts, the sodium, potassium, ammonium, and alkylolammonium salts, forexample. Specific examples are: sodium lauryl sulfate, sodium tallowalkyl sulfate; sodium salt of sulfonated alpha-tridecene; potassiumN-methyl-N-lauroyl tauride; triethanolammonium tetrapropylbenzenesulfonate; sodium (linear) dodecyl benzene sulfonate.

Examples of other nonionic organic detergents which can be used in thecompositions of this invention, if desired, are: polyethylene oxidecondensates of alkylphenols where in the alkyl group contains from 8 to15 carbon atoms (e.g., -t-octylphenol) and the ethylene oxide is presentin a molar ratio of ethylene oxide to alkylphenol in the range of 8:1 to20:1; condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylene diamine wherein themolecular weight of the condensation products ranges from 5000 to11,000; the condensation products of from about 5 to 30 moles ofethylene oxide with one mole of a straight or branched chain aliphaticalcohol containing from 8 to 18 carbon atoms, e.g., condensation productof 6 moles of ethylene oxide with one mole of lauryl alcohol; higheralkyl di-lower alkyl amine or phosphine oxides, e.g.,dodecyldimethylamine oxide or dodecyldimethyl phosphine oxide; alkylmethyl sulfoxides such as dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly de scribed as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight chain or branched and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic water solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate. Examples of compoundsfalling within this definition are sodium 3-dodecylaminopropionate,sodium 3(N-methyl-N-hexadecylamine) 2-hydroxy propane-1- sulfonate 'andits dodecyl homolog, sodium 3-dodecylaminopropane sulfonate, sodiumdodecyLbeta-alanine, sodium N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof United States Letters 'Patent Number 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching ofUnited States Letters Patent Number 2,438,091, and the products soldunder the trade name Miranol and described in United States LettersPatent Number 2,528,378.

Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radical may be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 10 to about 18 carbon atoms and one contains an anionic watersolubilization group, e.g., carboxy, sulfo, or sulfato. Examples ofcompounds falling within this definition are:3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate and thecorresponding dodecyl and tetradecyl homologs and3-(N,N-dimethyl-N-dodecylammonio)-propane-1-sufonate and thecorresponding hexadecyl and tetradecyl homologs.

The detergent compositions of this invention can also contain any of theusual adjuvants, diluents and additives, for example, perfumes,anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents,dyes, fluorescers, suds builders, suds depressors and the like, withoutdetracting from the advantageous properties of the composition.

Certain mixtures of the sulfonediimines of this invention andalkylbenzene sulfonates exhibit superior and unexpected mildnesscharacteristics. In certain ranges, and under comparable conditions ofexposure, mixtures of these two detergent compounds in aqueous solutionare milder to the skin than either one alone. Thickening, dryness andcracking of the skin of test animals under exaggerated exposures tosolutions of such mixtures are markedly reduced and in some casesdisappear in com,- parison to similar exposures to solutions of eitherof the actives alone. This mildness effect is very advantageous sincecombinations of the alkyl benzene sulfonates and sulfonediimines incompositions of the present invention are eflicient detergents. Thecleansing compositions of this invention having superior mildnesscharacteristics (comprise mixtures of alkylbenzenesulfonates havingalkyl radicals ranging from about 9' to about 15 carbon atoms and thesulfonediimines of this invention, the natio of the respectiveingredients being in the range of about 5:1 to about 1:10.

The alkylbenzenesulfonates in compositions of this invention are thewater-soluble salts, such as the alkali metal (e.g., sodium andpotassium), ammonium and substituted ammonium -(e.g., triethanolamine)salts, of sulfona-ted alkylbenzene in which the alkyl radicals rangefrom about 9 to about 15 carbon atoms. Especially preferred for useherein are the linear alkylbenzenesulfonates, for example, lineardodecylbenzene sulfonate. Also useful herein are alkylbenzenesulfonateshaving their alkyl chain derived from propylene, for exampletetnapropylenebenzenesulfonate. These alkylbenzenesulfonates arecommonly used as a sodium salt.

In the testing of detergent compounds and compositions for mildness andfor the unexpected mildness eflect, skin is contacted by immersion orother means with a solution of the detergent under standardizedconditions as more fully described below. A 1 to 10 se'ale is used torate the effects of prolonged exposure on the skin. Grade 10 representsideal or perfect skin (soft, smooth and flexible) and the effect ofatheoretically perfectly mild detergent; Grade 1 represents severelyirritated Other values represent gradations of severity between theseextremes. Grade 1 in a guinea pig immersion test indicates severelythickened, dry, cracked and bleeding sikn, i.e., extreme irritation.Grade 1 in exaggerated tests on human subjects indicates severe rednessand dryness of the skin. Thus, the exaggerated exposure tests on animalsare much more extreme than those conducted on human subjects.

There is a good correlation between the results of exaggerated exposuretests on animals and the results of normal use tests on humans; theformer can be relied on to grade the relative mildness of detergentstoward the human skin.

-As used in the examples, the graded guinea pig immersion tests consistof immersing the animal up to the thorax in the test solutions at 37 C.for a 4% hour period per day for 3 consecutive days. The animals aregraded 3 days after the last immersion. The grades given in the examplesare the average of the results on not less than three animals. It 'willbe understood by those with experience in biological experimentsthat.there is variation in the reactions of individuals, within a group,to expose the chemical solutions; this is true whether the individualsare guinea pigs or humans.

The following examples are illustrative of the present invention and arenot to be construed in any way as limiting its scope.

6 EXAMPLE 1 Preparation of methyl dodecyl sulfonediimine C H: NH

izHn NH In a two-liter three-neck flask equipped with a 10 mm. diametergas inlet tube, mechanical stirrer, and drying'tube, were placed 86.4grams (0.400 mole) methyl dodecyl sulfide and 1300 ml. dry acetonitrile.A chloramine-ammonia mixture generated according to the previouslydescribed Sisler technique was passed into the flask at 05 C. duringfour one-hour periods. The chloramine was passed into the flask at therate of 0.4 mole per hour or 1.6 moles over the entire four-hour period.Ammonia in admixture with the chloramine was passed into the flask atthe rate of 4.25 moles per hour; the mole ratio of ammonia to chloraminein the mixture was about 10.6:1. After each one-hour gas addition periodthe ammonium chloride which precipitated in the chloramine generator wasremoved from the system. The reaction was then stirred for 15 hours at 0C. and filtered cold.

The filter cake was extracted thoroughly with isopropanel and the bulkof the isopropanol was removed in vacuo using a rotary evaporator. Theresidue was then redissolved in isopropanol and washed three times with50% aqueous potassium carbonate. The isopropanol was again evaporatedand the solid residue recrystallized from ethyl acetate to provide 46grams of substantially pure methyl dodecyl sulfonediimine.

A similar preparation was carried out exactly as above except that 1300ml. of isopropanol was substituted for the 1300 ml. dry acetonitrileemployed as a reaction solvent above. After purification thispreparation yielded 44 grams of methyl dodecyl sulfonediimine.

Methyl decyl sulfonediimine was prepared from 0.3 mole methyldecylsulfide and 1.2 mole chloramine in admixture with about 12.8 molesammonia in acetonitrile following the same procedure described above forthe dodecyl homolog. The resulting reaction mixture was purified toyield 29.5 grams of methyl decyl sulfonediimine.

Methyl tetradecyl sulfonediimine, methyl hexadecyl sulfonediimine andethyl octadecyl sulfonediimine can be prepared by employing the aboveprocedure with the corresponding dialkyl sulfide in isopropanol solvent.

The cleaning ability of the above-synthesized compounds in the washingof clothes was comparable to that of tetrapropylenealkylbenzenesulfonate.

The following aqueous solutions (distilled water) were compared ingraded guinea pig immersion tests:

Test solution: Grade Sodium dodecylbenzenesulfonate (tetrapropylene)(0.2%) 3 Methyl dodecyl sulfonediimine (0.2%) 2 Sodiumdodecylbenzenesulfonate (tetrapropylene) (0.2% +methyl dodecylsulfonediimine (0.2%) 9 Similar results are achieved when lineardodecylbenzene sulfonate or other of the above-mentionedalkylbenzenesulfonates are substituted for the above tetrapropylenedodecylbenzenesulfonate and/or other sulfonediirnines of this invention,for example, methyl decyl sulfonediimine, methyl tetradecylsulfonediimine, methyl hexadecyl sulfonediimine or ethyl octadecylsulfonedimine are substituted for the methyl dodecyl sulfonediimineabove.

A significant unexpected mildness effect is apparent in the solution ofa mixture of alkylbenzenesulfonate and the sulfonediimines of thisinvention in a 1:1 ratio as compared to solutions of the individualdetergents alone.

The following examples illustrate detergent compositions containing thesulfonediirnines of this invention which can be used under conditions ofordinary usage to clean, for example, soiled clothing or soiled dishes.

EXAMPLE II Solid-Granules Percent Methyl dodecyl sulfonediimine 17.5Sodium tripolyphosphate 50.0 Sodium silicate (Na O:SiO =1:2.5) 10.0Sodium sulfate 17.5 Moisture 5.0

EXAMPLE III Compressed granules-Tablet Percent Methyl hexadecylsulfonediimine 31.0 Tetrasodium pyrophosphate 52.0 Trisodium phosphate10.0 Moisture 7.0

EXAMPLE IV Solid-Granules Percent Ethyl octadecyl sulfonediimine 32.2

Trisodium ethane-l-hydroxy-l,1,2-triphosphonate 64.0

Moisture 4.0

EXAMPLE V Solid-Granules Percent Methyl dodecyl sulfonediimine 10.0Sodium (linear) dodecylbenzenesulfonate 10.0 Sodium tripolyphosphate50.0 Sodium sulfate 30.0

EXAMPLE VI SolidGranules Percent Methyl tetradecyl sulfonediimine 10.0Sodium (tetrapropylene) dodecylbenzenesulfonate 10.0 Sodiumtripolyphosphate 50.0 Sodium sulfate 30.0

EXAMPLE VII SolidGranules Percent 3-(N,N-dimethyl-N-hexadecylammonio)propanel-sulfonate 20.0 Methyl hexadecyl sulfonediimine 25.0 Sodiumtripolyphosphate 35.0 Sodium carbonate 10.0 Sodium silicate (Na O:SiO-=1:2.5) 5.0 Moisture 5.0

EXAMPLE VIII SolidGranules Percent Methyl dodecyl sulfonediimine 20.0Sodium tallow alcohol sulfate 10.0 Trisodiumethane-l-hydroxy-1,1-diphsph0nate 20.0 Sodium tripolyphosphate 10.0Sodium nitrilotriacetate 10.0 Sodium sulfate 8.0 Sodium silicate (NaO:SiO =1:2.5) 11.0 Moisture 11.0

EXAMPLE IX Liquid Percent Methyl decyl sulfonediimine 5.0 Sodium salt ofS0 sulfonated 1:1 Weight mixture of dodecene and alpha-tetradecene 10.0Tetrapotassium pyropyhosphate 19.0 Sodium silicate (Na O:SiO =1:1.6) 3.8Potassium toluene sulfonate 8.5 Carboxymethyl hydroxyethyl cellulose .3Water Balanc 8 EXAMPLE X Liquid Percent Methyl dodecyl sulfonediimine6.0 Sodium (linear) dodecylbenzenesulfonate 6.0

Tetrapotassiu-m propane-1,1,3,3-tetraphosphonate 20.0

Sodium (linear) tridecyl benzenesulfonate 10.0

Dodecyldi methyl phosphine oxide 5.0 Coconut oil soap 5.0 Sodiumtripolyphosphate 50.0 Tetrasodium ethylene diamine tetraacetate 20.0

Good detergency effects are also obtained when in the above examples thefollowing builders are substituted for those employed in such examples:tripolyphosphates; pyrophosphates; ethylene diaminetetraacetates;N-(2-hydroxyethyl)-ethylenediamine triacetates; nitrile triacetates;N-(2 hydroxyethyl) nitrilodiacetates; phytates; polycarboxylatepolymers; and polyphosphonates.

It will be appreciated that the sulfonediimine compounds used in thepresent invention can be incorporated into many other liquid or granulardetergent compositions with suitable adjustments being made in the othercomponents.

Materials which are considered normal and desirable additives in liquidor granule detergent compositions can be added to the compositions ofthis invention without adversely affecting or modifying basic cleaningcharacteristics. For example, a tarnish inhibitor such as benzotriazoleor ethylene thiourea may be added in amounts up to about 1%.

What is claimed is:

1. A sulfonediimine having the structural formula wherein R is analiphatic radical containing from about 10 to about 18 carbon atoms andR is selected from the group consisting of methyl and ethyl radicals.

2. Methyl decyl sulfonediimine.

3. Methyl dodecyl sulfonediimine.

4. Methyl tetradecyl sulfonediimine.

5. Methyl hexadecyl sulfonediimine.

References Cited UNITED STATES PATENTS 3,379,759 4/1968 Cogliano et al.26055l CHARLES B. PARKER, Primary Examiner.

D. R. PHlLLIPS, Assistant Examiner.

US. Cl. X.R.

1. A SULFONEDIIMINE HAVING THE STRUCTURAL FORMULA R-S(=NH)2-R'' WHEREINR IS A ALIPHATIC RADICAL CONTAINING FROM ABOUT 10 TO ABOUT 18 CARBONATOMS AND R'' IS SELECTED FROM THE GROUP CONSISTING OF METHYL AND ETHYLRADICALS.